Lubricant



Patented Ma. 11, 1947 LUBRICANT Carl F. Prutton, Cleveland, Ohio, assiznor to The Lubri-Zol Corporation, Wickliife, Ohio, a corporation of Ohio No Drawing. Application December 19, 1940, Serial No. 370,839

1 Claims.

This application is a continuation-in-part of my co-pending application, Ser. No. 216,153, filed June 27, 1938, which in turn was a continuationin-part of my co-pending application, Ser. No. 760,038, filed December 31, 1934, now Patent No. 2,121,825, which was in turn a continuation in part of co-pending applications Serial Nos. 635,701; 635,599 and 679,594, now respectively Patent Numbers 1,986,651; 1,986,645 and 2,051,744; also application Ser. No. 737,070, filed July 26, 1934, and application Se No. 158,531, filed August 11, 1937, now Patent No. 2,121,824.

The above identified applications disclose the use, in the field of lubrication, of halogenated carbon ring compounds. Said applications more specifically disclose the fact that certain of the above-named type of compounds, when added in very small amounts to a lubricating oil such as a mineral oil, impart extreme pressure" characteristics thereto, 1. e., a lubricating film formed of such material, when occurring between relatively moving metallic bearing surfaces is capable of withstanding considerably greater pressures per unit area, before such film is ruptured, than previously known lubricants, particularly mineral oil when used in its pure state.

This invention relates to the discovery that certain compounds, among which are included certain compounds covered by the broad class, as defined in my above identified applications, are likewise particularly useful in the field of lubrication.

Certain of the compounds to which the present invention relates are particularly useful as means for imparting extreme pressure characteristics to lubricating compositions generally, such as lubricating oils; as means to impart certain characteristics to lubricating compositions not ordinarily possessed thereby and also to function as primary lubricants either in their pure state or combined with other lubricating constituents.

It is a principal object of my invention, therefore, to provide, for use in the field of lubrication, certain materials having a wide variety of usage and by the use of which certain results may be obtained which have heretofore been impossible.

Other objects of my invention will appear as the description proceeds.

To the accomplishment of the foregoing and related ends, said invention, then, consists of the features hereinafter fully described, and particularly pointed out in the claims, the following description setting forth in detail certain embodiments of the invention, these being illustrative, however, of but a few of the various ways in 2 which the principle of the invention may be employed.

Broadly stated, this invention contemplates the use in the lubricating field of such materials as may properly be defined as substituted organic ring compounds containing an aliphatic substituent and an element in addition to carbon and hydrogen.

The element in addition to carbon and hydrogenabove referred to will advantageously be an element other than oxygen, and for certain uses an element other than oxygen or nitrogen. This additional element may be present with either oxygen or nitrogen, and for certain uses preferably with oxygen.

From the foregoing statement defining broadly the addition agents contemplated for use in the present invention, it will be observed that the molecule of such addition agents contains:

(a) An aromatic nucleus; (b) An aliphatic substituent; and (c) Another element.

.mean to include all substituents which either consist of or contain one or more of the following elements:

The halogens, e. g.,

Chlorine Bromine Fluorine 1 Iodine Sulphur Phosphorus Arsenic Nitrogen The metals When sulphur is present as part of a substituent group, it may, for example, be present in any of the following:

(1) Mercapto 6- (2) sulphide when the radiclc is directly attached to a O atom. (33) Polysulphide where 2 equals at least 2.

4 Thiocynnate (40M) 3 I Q ('i') (5) Thioketone (6) Thin-aldehyde (7) 'lhlo-carboxyl (8) Thin-ester -(E SH) and (T (57 Ci) When the inorganic substituent also contains oxygen in addition to the characterizing inorganic element, such substituent may be any of the following, for example:

(1) (-o-M where M is a metal) (2) Amide and substituted amide (i or (a) Additional examples of inorganic substituents are those thio substituents which correspond to the oxygen containing substituents given immediately above under (1), (2), (3) and (4), but in which one or more of the oxygen atoms in any of the substituents of (1), (2), (3) and (4) above are replaced with sulphur, for example,

Mercaptide (SM) Thioamide, etc.

The following are specific examples of metals which may be included in the foregoing list comprising the inorganic substituent:

Sodium Manganese Potassium Aluminum Ammonium Chromium Lithium Tin Magnesium Lead Calcium Copper Strontium Cadmium Barium Bismuth Cobalt Silver Zinc Mercury Nickel Vanadium From the foregoing, it will be observed that component C, i. e. the third component of the molecule of the addition agents of the present invention, is preferably an inorganic radicle which contains oxygen or sulphur, and in addition preferably contains a metal.

The oxygen or sulphur acts as a means of attaching the addition agent to metallic surfaces so that it will be most effective for the protection of such surfaces, especially under conditions of 4 boundary or thin film lubrication. Conditions which produce boundary or thin film lubrication are those in which the bearing surfaces are not completely separated by a fluid film. This may result from high unit loading, e. g. in excess of ten thousand pounds per square inch; low speeds; high temperatures; or a deficiency of lubricant.

This invention also contemplates the use in the field of lubrication of'compounds which may be defined as products of reactions taking place in the presence of certain catalysts, such as anhydrous aluminum chloride, between certain unsaturated organic compounds and organic ring compounds.

By reference to certain of my above-identified co-pending applications and the applications with which they were related by co-pendency, certain groups of compounds will be found which come I within the scope of the present invention, namely, the halogenated, or more specifically, chlorinated homologs, (i. e., compounds carrying alkyl sidechains) of benzene, naphthalene, and diphenyl. Examples of these compounds will be found to include halogenated, or more specifically, chlorinated, toluene, methyl naphthalene, phenyl toluene, and xylene. 1

.With reference to the compounds which may be prepared by the reaction between certain unsaturated organic compounds and organic ring compounds in the presence of catalysts such as anhydrous aluminum chloride, the following is an outline of the procedure which may be followed and the materials which may be employed in such procedure.

CATALYSTS The catalysts, which it is possible to employ in carrying out the condensation reaction to form certain of the products contemplated for use in the lubrication field by this invention, may be broadly defined as any catalysts which promote condensation reactions of the above type; specific examples of suchcatalysts are anhydrous aluminum chloride, anhydrous ferric chloride, and the addition products formed in the reaction of such anhydrous chlorides with olefines such as ethylene; for example, the addition product of anhydrous aluminum chloride and ethylene, AlClz-CzHe. Generally speaking, the broad class of catalysts capable of being used are those well known in the art as being substantially the equivalent of anhydrous aluminum chloride.

UNsA'ru'RArEn ORGANIC Comrounns The unsaturated organic compounds forming one component of the condensation reaction may be conveniently defined as compounds containingat least one pair of multiple-bonded carbon atoms, such as the groups CH=CH.- and --C-=-C. This class of compounds includes those which may be described as members of the olefine and acetylene series together with derivatives of them formed by substitution.

When the reaction components are an unsaturated organic compound of the olefine type and a ring compound of the aromatic type, the resultant product is probably in the nature of a homolog 'of the aromatic compound, e. g., an alkylated aromatic compound, and'the reaction may be expressed as follows:

where R and R" are organic radicles Or hydro gen and R is an aromatic radicle.

those produced by polymerization oi the oieflnes.

The di-oleflnes or other poly-olennes such as m Unnamed ,ddl'u" Vinyl lactic acid (e. g. butylenes, pentenes, hexenes, etc.) produce r i' similar products of a. more complex nature and. Xiigtg'ifi for certain purposes are of a preferred type. 5 Certain other unsaturated organic compounds that? are capable of producing products of the type contemplated. A preferred type er unsaturated $312223? Md com ound is one containing one or more long m'li'mnlv chain structures such as the normal alkyl groups 10 hmigfirig cld which contain more than three carbon atoms and preferably more than ten; for example, the i gt i fie' i mrboxyiluciu lauryl, cetyl, ceryl, and melissyl groups. when (a Unsaturated anhydridas: such long chain" unsaturated compounds are gggfiggfiggg'gg, used. or when the unsaturated organic com- 15' Citraconicanhydride pounds are contained in a complex mixture, it gggig g ggl'ggfl g may be desirable to use AlC1JC2H4 as the catalyst gllutgci mic a'nhr iride rather than A1013. g g g gg -ggggg Ydflde A complex mixture of unsaturated compounds 7 Unsaturated estors,e.g.,

Boric acid is often preferred to a single pure compound, (a) Estgss oi unsaturated acids (e. g. those listed under (s) and a pre erred source of such compounds is a va as we as unsaturated aromatic acids such as ci nami a found in the products of the so-called "cracking" al oholsf o r oiii h i dr y fiflirioui'i s iiiciu fifi process as applied to petroleum products; for gg ff ggfg iz f of such alcohols and hydroxy example, cracked gasoline, cracked kerosene, Methyl alcohol cracked paraflin or other waxes, cracked heavy Ethy al ol oflsec ianist? o 0 s Unsaturated organic compounds other than Amyl alcohols hydrocarbons may also be used and may, for 332;? 32 some purposes, give improved results. Included gi f among such unsaturated compounds are the fol- 1 f i?: :i' lowing 018.8585: Amyl cyclohexanol Benzyl alcohol Table 1 Furiuryl alcohol Tetrahydrofuriuryl alcohol (A) Oxygen-bearing substitution products (for further classification Ethylene glycol and examples see Tables Nos. 2 and 3 below). p l ne ly l (B) Halogen-bearing substitution products. iethi'lene sl wl (C) Other substitution products such as those containing the follow- Glycerol ing su bstituent groups: Erythrltol Amino, and substituted amino groups Phenol Imi o Polyhydroxy-berizenes Azo Alkvlated phenols Hydroazo Naphthols Hydrating 40 Unsaturated alcohols (e. g. those listed under (1) iitrileil above).

9 (b) Esters of unsaturated alcohols (e. g. those listed unde gffififlgg (1) ab e) it priz n cid either aliphatic o; Polysulpmde ggltrlnsizrtig or with inorganic acids. Examples of such Thiocyanate Isothiocyannte a. Aliphatic acids, including Dithiocarboxylic acids (also ester and salt groups derived Saturated acids such as:

t ere Acetic acid N crn: This invention contemplates the use oi compounds containing Propiqnic {was more than one substituent group. In such cases the compound W F may belong in two or more of the above classes. ia lricacidsd 8 [Ill 10 80! Examples of the oxygen-bearing compounds g r qg xa is sex are as follows. g 3

actic aci Table N0. 2 Giycolic acid U am Wi l h I Malonic acid xiii y fl eithg'flgic hl loi gfi u mted acids, such as those listed under (5) sec 0 c -o zfonyl alcohol Aromatic acids. including:

9 alcohol Benzolc acid Propargyl alcohol Phthal ic ac ds (2) Unsaturated aldehydes, e. g., sallcyllcppld Acrolein Anthranilic acid grotogaldehyde Cinnamic acid exa ienal Cycle-aliphatic acids includin g c t a t rienal co gaphghgniillaacid id x c a e Pmpargync aldehyde Hetero: cl i c ri id: i 2 (3) Unsgtlurated ketones, e. g., Furgic acid c u mg.

Dilghgc ltggem Pyrrol carboxyllic acids Mesitv] oxide Pyridine carboxyllic acids Phorchc Inorganic acids, including:

Vinyl lauryl ketona Hydro-halogen acids Acetylenic ketones (e. g. R-CEC-CO-R'), such as: Olly-halogen acids Ailvlene methyl ketone Sulphurous acid Allyleue lauryl ketone Sulphuric acid (3a) Ketenes Thlosulphuric acid Ketene Carbonic acid Acetyle kotene Thiocarbonic acids (4) Unsaturated ethers, e. g., 7 Hy rogen sulphide Di-vinvl ether Phosphorous acid Di-allyl ether Thiophosphorous acids Ally] ethyl ether Phosphoric acid Vinyl ethyl ether 'Ihlopbosphoric acids Ally] iso-arnyl ether yimi cid Ally! laurll other Thiocyanic acid Propargyl ethyl ether 7 Hydrocyanlc acid a Saltsoiunsaturated ids, inelud the Ammonium ands uhstituted a monium Salt unsaturated acids generally, and more specifically of such acids as those listed under above and 01 unsaturated aromatic acids. 7

In addition to the compounds listed above, commercial products comprising complex mixtures of unsaturated oxygen-bearing organic compounds may be used as the unsaturated" reactant. Examples of such materials are the fatty oils oi. unsaturated character, e. g.,

Castor oil China-wood oil Linseed oil Menhaden ilsh oil Rape seed oil Soya bean oil Sperm oil Additional material, for use as the "unsaturated reactant in the condensation, may be derived from any of the above fatty oils are, e. g., (i) Acids, extracted from the oils by direct hydrolysis, or by saponi' flcation and subsequent hydrolysis, or otherwise.

(2) Esters, produced by esteriiylng the acids of (1) e. g. to form esters analogous to any of those listed under (7) in Table No. 2.

(3) Soaps, produced by saponii'ying the oils directly or by neutralizing the acids oi (l) with alkalies, e. g. to form salts analogous to those listed under (s) in Table No. 2.

The unsaturated oxygen compounds are of particular importance and may, therefore, be classified in further detail according to the nature of the attachment of the oxygen atom to the molecule, viz:

Table No. 3

I. Directly attached to one or more carbon atoms, as in the case of:

(1'; Ethers and analogous compounds. (2' Compounds containing the radicle, such as alcohols and other derivatives oi carbinol (mcludmg phenols, cresols, naghthols, etc.). (3') Com ounds containing the carbonyl =0 radicle, suc as amides, aldehydes ketones, organic acids, esters and salts of organic acids (including such salts of both inorganic and organic bases), thio-acids and Al'senites Hypochlorites Phosphites Thiophosphates Thio hosphites -hy xylamines orates II. Indirectly attached through the means of some other atom,

a. g., in the Arsenate Chlorate Chlorite Cyanate u-Hydroxylamine N trate form of an inorganic radicle, e. g.,

Sulphite Sulphinic acid Sulphone Suiphonic acid phoxide 'lh;.ophosphate Th..ophos hite Th o-sulp ate (Non: This class includes salts of organic bases with inorganic cry-acids).

In addition to the unsaturated comp unds above described, certain unsaturated cycllcc'ompounds are also of use, such as the cyclo-oleflnes (e. g. cyclo-hexene) and derivatives of them. Examples of such unsaturated cyclic compounds are:

Oxygen-containing compounds:

Alcohols Terpineol Isopulegol Dihydrocai-veol Pinocarveol Aldehydes Ketones Puiegone Piperitone Carvone Euearvone Ionone Pinocarvonc Verbenone Carvenone Ethers Pinol Tetrahydro-anisole Tetrahydro-phenetole Acids Laurolenic acid Ohaulmoogric acid Hydnocarpic acid Tetrahydrobenzoic acid Tetrahydrotoluic acids Tetrahydro-x lic acids Methyl cyclo exylidene acetic acid Fural acrylic acid Fural malonic acid Benzal malonlc acid Benzal proplonic acid Benzal lactic acid Abietic acid Commercial products comprising complex mixtures of unsaturated cyclic organic compounds may also be used, c. g.,

Turpentine Pine oil Oncamc Rmo Comoimns The organic ring compounds may be classified as follows: I

Table No. 4

A. "Carbon ring type compounds- (a) 01' the aromatic (i. c. benzenoid) or allied type, including benzene, naphthalene, anthracene, and their derivatives; also compounds of the bridged ring type, such as the tcr her, and related compounds.

(0) 01 the c ass including the cycloparaiilns, cyclo-oleiines,

etc. Examples of this class are the following:

(1) Hydrogenation products of benzene, (e. g. cyclohexane, cyclohexene, cyclohexadienc). (2) Hydrogenation roducts of naphthalene, (e. g. {lecahydronap thalene, tetrahydronaphthane, etc.) (3) Naphthenes, naphthenic acid, etc. (c) Oi the mixed type such as hydrindene, hydranthracene,

B. "Heterogeneous ring" type compounds (i. e. heterooyclic) (a) Of the aromatic (benzenoid) or allied pyridine, quinoline, etc., and their derivatives. (0) Other types such as iuran, thiophene, pyrrole, etc., and

their derivatives.

type including The organic ring compounds which are preferred for my purpose are those of the aromatic type (A (a) and B (a) of the table above). These may be further classified as follows:

Table No. 5

I. Hydrocarbons- A) Benzene and its homologs such as toluene, xylene,

cymcne, ethyl-benzene, mcsitylene.

(B) Polyphenyls such as diphenyl. diphenyl benzene, and homologs of them such as o-phenyl toluene, poly-ethyl diphenyls. propyl diphenyl.

(O) Condensed ring hydrocarbons (l) Naphthalene and its homologs, such as the methyl naphthalenes, ethyl naphthalenes, propyl naphthalenes.

(2) Phenanthrene and anthracene and their homo- .logs such as the monoand di;methyl. and propyl and iso-propyl, substitution products, e. g. retene.

(3) Chrvsene and picene and theirhomologs.

(D) Compounds resulting from substitution of aryl groups in compounds of classes (A), (B) and (C), e. g., di-benzyl, di-naphthyl, phenyl naphthalene, the polyphenylmethancs, etc.

(E) Bridged ring hydrocarbons such as certain of the terpenes and related compounds including pinenc, camphene and limonene.

II. Heterocyclic compounds of the aromatic or allied type such as pyridine, quinoline, thiophene, etc., and their derivatives.

III. Substitution products (other than hydrocarbon homologs) of compounds of classes I and II, including:

(A) Oxygen-bearing substitution prod ucts. (See Table N o. 6 below, for further classification.)

(B) Halogen-bearing substitution products.

(C) Other substitution products, such as those resulting from substitution of the following groups:

Amino, and substituted amino groups Imino Azo Hydrazo Hydrazine Nitrile Isonitrile Mercapto Sulphide Polysulphide 'Ihiocyanate Isothiocyanate Dithiocarboxylic acids (also ester and salt groups derived therefrom) IV. Derivatives of the compounds included in Classes I, II, and III resulting from addition reactions, such as hydrogenation, haiogenation, etc. Examples of such compounds are the hydro-naphthalenes, phenyl cyclohexane, phenyl cyclohexanol, cyclohexyl phenol, naphthalene tetrachloride.

Attention is called to the fact that certain of the compounds may belong to more than one class; as, for example, the halogenated phenols which belong in Class III (A) and III (B) or the halogenated amino phenols, Class III (A), (B) and (C).

The oxygen-bearing aromatic compounds (Class III (A) of Table No. 5) are of particular importance, and are, therefore, classified in further detail according to the nature of the attachment of the oxygen to the molecule, viz:

Table No. 6

I. Directly attached to one or more carbon atoms, as in the case oi:

(1) Ethcrs and analogous compounds. (2) Compounds containing the radicle, such as alcohols and other derivatives of carhinol (including phenols, cresols, naphthols, etc.) (3') Compounds containing the carbonyl C= radicle. such as amides, aldehydes, ketones, organic acids. esters and salts of organic acids (including such salts or both inorganic and or anic bases), thio-acids and esters and salts of thio-acids. (4') Compounds in which oxygen forms a part of the ring structure, e. g. iuran and its derivatives, etc. (5) Compounds with an inorganic radicle where the oxygen is directly attached to a carbon atom, e. g.,

Arsenites Hypochlorites Phosphites Thiophosphates 'Ihlophosphites fl-Hydroxylamines Borates I1. Indirectly attached through the means oicomc other stem 1. o. in thiform of an inorganic radiclc, o. g.,

Arscnate Chlorate Chloritc li l d lamin uroxy c Nitntc Nitrite Nitro Nitroso Oiime Perchlorate Phosphate Sulphate Sulphite Bulphinic acid Sulphone Sulphonic acid Suiphoxide Thiophosphatc 'Ihlophosphite Thlosulphato (N on: This class includes salts oi organic bases with inorganic cry-acids.)

For specific examples of oxygen-bearing aromatic compounds, reference may be had to the table beginning on page 6 of my co-pending application Ser. No. 737,070, filed July 26, 1934. These examples include both the unhalogenated compounds listed and the halogenation products of them.

The classification 01' the unsaturated compounds and of the organic ring compounds is sufliciently broad so that the two classes of compounds overlap. There are certain compounds belonging to both classes, as indicated by this overlapping, which are suitable for either use; for example, an aromatic compound containing a. double-bonded pair of carbon atom in a side chain may be used either as the unsaturated compound or as the organic ring compound in Table No.. 7

Stilbene Styrene Chlor styrene: Vinyl phenols Cinnamic alcohol Cinnamic aldehyde Vinyl anisoles Allyl phenyl ether Allyl phenols Aromatic esters of unsaturated acids, e. g.,

Benzyl acrylate Ben zyl olcate Phenyl oleate Esters oi unsatutrated alcohols with aromatic acids, 0. g..

.nzoa e Oleyl benzoata Allyl salicylate Unsaturated aromatic acids, 0. g.,

Couinaric acid Cinnamic acid Esters or unsaturated aromatic acids (including coumaric and cinnarnic acids). e. g.,

Methyl cinnamate Lauryl cinnamate Benzyl cinnamate Ally] cinnamato Oleyl cinnamate I Salts of unsaturated aromatic acids (including coumaric and cinnamic acids) with:

(0) Inorganic bases, 0. g., to form salts of:

Ammonium Sodium Calcium Aluminum M agnesiuin Zinc Lead (6) Organic bases, e. g.,

Ethyl amines Ethanol amines, such as tri-ethanol amine Aromatic amines, such as aniline The following table gives typical examples of the unsaturated compounds and of the organic ring compounds which are suitable for use in carrying out the above reaction in the production of compounds suitable for use in the field of lubrication in accordance with this invention.

But i ricinoleate Met yl ricinoleate Lauryl ricinoleate Chlor-benzenes Chlor-diphenyls Chlor-diphengl others ample, the products resulting from the reaction "Tri-allyl phosphate Methyl oleate Chlor-benzop enones Benzyl oleate Benzonitrile Oleyl stearate Methyl salicylate Oleyl acetate Methyl chlorsalicylates Allyl stearate Allyl oleate Retene oil Ole l oleate Tar acids.

Ani ine oleate Triethanolamine olcate Calcium oleate Aluminum oleate Calcium ricinoleate Calcium linoleate Calcium stcarolate Methyl linoleate Methyl stearolate Lauryl propiolate Methyl cinnamate Allylene oxide Allylin 'letrachlorethylene Allyiamine Allyl amine acetate Allyl merca tan Ally] 0 ani e Allyl t iocyanate All i trisulfide Ch orbenzyloleates Chloracetylenes Chlor acrylic acids Chlor crotonic acids Chlor oleic acids Tri-allyl 1Phosphite Castor o Rape seed oil ganic ring compounds are, for certain purposes,

superior to corresponding oxygen-free compounds, probably as a result of the tendency of oxygen-bearing compounds to be strongly adsorbed on metal surfaces. It is to be noted that the products of reaction of oxygen-bearing unsaturated compounds with aromatic compounds are to be preferred for the same reasons.

Included among the examples of such preferred compounds are the condensation products resulting from condensation of metallic salts of unsaturated fatty acids with aromatic compounds. Such condensation products are the salts of aromatic substituted fatty acids. Specific examples of these are the condensation products resulting from the condensation of aluminum oleate with the aromatic compounds listed above under Typical organic ring compounds.

Examples of such condensation products are the following:

Aluminum salts of Phenyl stearlc acid Tolyl stearic acid Xylyl stearic acid Naphthyl stearic acid Xenyl stearic acid Phenoxy phenyl stearic acid chlorphenyl stearic acid ing) of unsaturated compounds such as cracked kerosene with halogenated oxygen-bearing aromatic compounds such as chlorinated diphenyl ether, or the chlor aryl phosphates, e. g. the tri-chlorphenyl phosphates.

In addition to the halogen-bearing compounds, organic derivatives of any of the inorganic oxyacids are also suitable in producing products useful in extreme pressure lubrication. Such products may be formed by the reaction either of unsaturated aliphatic derivatives of such acids (e. g. allyl esters of sulphuric and phosphoric acids) with organic ring compounds, or of aryl derivatives of such acids (e. g. triphenyl and tricresyl phosphate) with unsaturated compounds or by treating a suitable condensation product with a suitable reagent.

In making use of halogen-bearing compounds, for some purposes, it is desirable that the halogen be attached to a carbon atom which is part of a benzenoid ring structure to prevent the corrosive effect resulting from the easier hydrolysis of other halogen compounds to form hydro-halogen acids. However, where very extreme pressures are encountered, it may be necessary to employ more chemically active materials. In the latter case, the halogen addition products of arcmatic compounds are particularly useful, because the de ree of reactivity of the combined halogen may be easily controlled.

It may be noted that halogen-bearing products may also be obtained by first reacting the unsaturated compound with the ring compound, and then halogenating. This is usually the preferred method of preparing halogen-bearing products except when it is desired to have the halogen attached to a benzenoid structure. It

will be noted that the above referred to halogenbearing compounds are of the type which contain a substantial amount of halogen.

Besides the halogen derivatives, other deriva-- tives contemplated hereby for use in lubrication may also be formed from the products of the condensation reaction (as well as from methylated organic ring compounds) for example, by esterification or saponification whenthe material is a. hydroxy compound -(e. g. an alcohol, phenol, or

. acid) or a base (e. g. a substituted ammonia), or

by treatment with organic or inorganic reagents e. g. PCla, POCI3,PSC13,P2S5,BC13, SzClz, S0012, Grignard reagents, etc.) when the organic material is of suitable type (e. g. hydroxyl-contain- An important group of compounds contemplated by this invention for use in the field of lubrication are methyl derivatives of organic ring compounds containing an element in addition to carbon and hydrogen. methyl derivatives of the organic ring compounds referred tov above, which derivatives also contain an element in addition to carbon and hydrogen and includes, as well, the methyl derivatives of the condensation products referred to above. Examples of this group of compounds are as follows:

This group includes Table No. 9

Additional specific examples of the addition agents of my present invention as found in my said parent application, Seria1 No. 737,070, are the halogen derivatives, and more specifically the chlorine-containing derivatives of the following compounds:

Aluminum phenyl mercapto stearate Aluminum phenyl stearate Calcium phenyl mercapto stearate' Calciu phenyl stearate Zinc phenyl stearate Sodium benzoate Sodium thiobenzoalte Zinc benzoate Additional specific examples disclosed in this parent application are the alkylated derivatives of the above compounds, including specifically the halogen derivatives, and more particularly the chlorine derivatives, of the following:

Allwlated sodium benzoate Alkylated sodium thiobenzoate Allwlated zinc benzoate In my aforesaid parent application, Serial No. 760,038 will be found listed as specific examples of addition agents of the present invention the condensation products of aluminum oleate with aromatic compounds, and specifically with naphthalene, anthracene, toluene, xylene, diphenyl, and phenanthrene, yielding for example the following compounds:

Aluminum naphthyl stearate Aluminum anthracyl stearate Aluminum toly1 stearate Aluminum xylyl steal-ate Aluminum xenyl stearate Aluminum phenanthryl stearate All of the above identified'specific examples of the addition agents of this invention are compounds which contain:

(a) An aromatic nucleus; 7 (b) An aliphatic substituent; and c) An inorganic substituent.

I It will be noted that the inorganic substituent in some cases is attached to the aliphatic substituent, as in the case of the salts of the aroall 14 matic substituted fatty acids, specifically aluminum phenyl stearate, and in other cases is attached to the aromatic nucleus as in the case of those examples which contain the chlor phenyl 7 group, for example, the condensation. product of chlorbenzene with aluminum oleate; the principal product of such condensation being the aluminum salt of chlor phenyl stearic acid.

It should be noted that the last named example contains a plurality of inorganic substituents, one of which is attached directly to the aromatic nucleus, and the other is attached to the aliphatic substituent.

In the foregoing identification of the various classes of addition agents useful in my present invention occur two classes of "compounds respectively characterized by the presence of the radicle 0-M, where M is a metal, and the radicle -SM, where M is a metal. These two classes of compounds may be generically defined as compounds containing the radicle X-M, where X is either oxygen or sulphur, and M is a metal.

It will be noted that these radicles may be attached at various points in the molecule and need not be attached exclusively to a hydrocarbon group; as in the mercaptides (previously identifled as examples of sulphur-containingaddition agents) but may as well be attached to a radicle which contains other substituents. For example, the X-M radicle may be attached to a II c radicle, where X is oxygen or sulphur, as in the form of the fil c-x-M radicle.

The radicle comprising the -X-M group may be attached either directly to the aromatic nucleus, as in the case of alkylated zinc benzoate or the radicle comprising the -X-M group may be a part of the aliphatic radicle, as in the case of the salts of aromatic substituted fatty acids, as for example, aluminum phenyl stearate.

The broad class of substituted organic ring compounds containing an element in addition to carbon and hydrogen and an aliphatic substituent constituting the materials useful as and in lubricants in accordance with my invention of which several different types of examples and methods of preparing the same have been given above,

when used as addition agents in lubricating compositions and lubricating compositions containing the same, will be found to have the followinguses and advantages:

In addition .to the advantages obtained by the use of certain products contemplated by this invention to increase the film strength of lubricating oils or as lubricants possessing high film strength, other advantages may be obtained as follows:

Certain of the compounds contemplated herein are extremely stable and therefore, resistant to decomposition, oxidation and gum-forming or sludge-forming reactions, especially when used in.

crankcase lubricants in internal combustion engines. In general, the class of products which contain long-chain structures and/r multiple chain structures, when present in liquids, reduce the rate of change of viscosity with the temperature and usually have a tendency to prevent precipitation of crystalline or gelatinous materials, such as waxes, on chilling. Lubricants comprising certainof such long and/or multiple chain products, therefore, have the advantages of improved viscosity index or lowered pour point.

It has been found that certain of the compounds above described, either alone or in combination with lubricating oils and/or other materials, such as organic oxygen compounds and organic halogen compounds, are capable of reducing the rate of wear of bearing surfaces, particularly during thin-film lubrication and especially when one of the bearing surfaces is of a so-called bearing-metal type such as brass, bronze, babbitt, lead-bronze, cadmium-silver, cadmium-nickel alloys, etc., these being generally classified as bearing metals containing a characterizing amount of lead, tin, copper, zinc, silver, nickel, cadmium, aluminum or telluriurn. This effect may, in som cases, be independent of the property also possessed by some of such materials for reducing friction, that is, reducing power losses in bearings.

Certain compounds which are particularly suitable for increasing the film strength of lubricating oils, when added in small amounts, for example, highly chlorinated naphthalene, have the disadvantage of being relatively insoluble in mineral oils, particularly at low temperatures. The oil solubility of these materials may be increased by alkylating, or adding an aliphatic substituent generally, for example, reacting them with unsaturated compounds, as disclosed herein, as for example, in reacting hexachlor naphthalene with ethylene to produce polyethyl chlor-naphthalenes which are completely miscible with mineral lubricating oils.

It will be observed that the class of materials contemplated for use as addition agents to lubricents in accordance with this invention has a relatively broad range as to stability and also as to chemical reactivity.

With regard to stability, the addition agent for a particular use should be selected from those suificiently stable not to be too quickly destroyed under operating conditions. For example, the thermal stability of an addition agent to be used in a crankcase lubricant should be relatively high so that the addition agent will not be too readily decomposed by contact with the heated metal surfaces to which the lubricant is exposed. Those materials which may be distilled without substantial decomposition, either at atmospheric pressure or under vacuum, at temperatures above 140 C. are often of advantage for such uses. Where the lubricant is intended for very high temperature applications, as for example, in the crank! cases of Diesel engines and aviation engines, the materials may advantageously be capable of such distillation at temperatures above 170 or even 200 C.

As to the re-actlvity of the addition agent and particularly with regard to its corrosive action, the addition agent should be selected for a particular use so that it will not react so readily with the metal surfaces with which it comes in contact as to damage them in normal use. However, when used in conjunction with a corrosion-inhibiting agent, e. g. in accordance with the teachings of my co-pending application Ser. No. 119,132, filed January 5, 1937, relatively highly reactive materials such as those which would normally be corrosive may be used to advantage, particularly where high film strength of the compounded lubricant is of special importance.

Since the addition of certain materials of the class including the above enumerated, which themselves are relatively non-viscous, will reduce the viscosity of the oil base to which the same are added, if a large percentage of such compounds is added, there will be a tendency to destroy thick-film lubrication because of the reduction in viscosity of the composition. If an excessive quantity of such compounds is added, all of the lubrication will then be of the thin-film type and, therefore, produce a decided increase in the total amount of friction developed. In such cases, it is advisable to employ the materialas an addition agent in amounts less than about 20%.

As previously indicated, the materials contemplated for use in accordance with my invention are often useful as lubricants themselves; however, due to their relatively high cost, generally satisfactory results may be secured by incorporating minor amounts of such materials with other lubricants suchas mineral lubricating oil. The particular properties of the lubricant desired will generally dictate the particular material selected for addition to the oil and the percentage in which the same is employed. In general, when preparing a lubricating composition for ordinary lubricating purposes, such as the lubrication of automobiles, i. e., crankcases and gear boxes, the concentration of the addition agent need not be greatly in excess of 20% in a refined mineral lubricating oil in order to provide an entirely satisfactory lubricant. In general, it will be found that percentages much less than 20% will be entirely satisfactory, i. e., in general, percentages necessary for the desired results will lie below 10%.

When compounding a lubricant to be used as a crankcase lubricant, it will usually be found that percentages ranging from .10% to about 2%, or 5%, will be entirely adequate for the purpose. The particular percentage range within which a certain material is added will, as above indicated, also depend upon the characteristics of such material, such as its activity and its tendency to react either chemically or physico-chemically with the bearing surfaces in order to provide the proper thin-film lubrication.

The foregoing discussion with respect to the percentages of the materials enumerated above which may be used in lubricating oil bases, such as mineral oil, have been given in connection with the preparation of a lubricant which is particularly characterized either by high film strength, low coefiicient of friction (oiliness) and the like.

, Many of the compounds contemplated for use 17 rosion, or in dissolving gummy and like deposits which occur when the lubricant containing the same is admitted to regions of high temperature such as in or adjacent to the combustion chamber. Such use is efficacious in overcoming ring. sticking tendencies in internal combustion engines. When the addition agents are added for this latter purpose, low percentages, usually much below those previously given, will be sufllcient. Percentages of from 1.0% or .1% to as low as .001% or less of certain of the compounds will-be found to be sufficient for particular purposes.

It will be observed that materials included within the contemplation of my invention as lubricants or addition agents to lubricants are generally possessed of extremely low volatility, even at elevated temperatures and certain of the compounds are characterized by the fact that they are stable and non-volatile even at extremely high temperatures which renders them particularly suitable for use as or in lubricants operating under conditions of high temperature; for example, Diesel engines and aviation engines.

When used in conjunction with a mineral lubricating oil, it is obvious that generally only such amounts of the addition agent may be included as are soluble in the specified amount of oil. By the term soluble, as herein used, it is intended to indicate the ability to form not only true solutions but also any form of substantially permanently homogeneous composition when incorporated in mineral oil. With most of the compounds there is usually little difficulty, especially if the incorporation is effected in the manner described in Cornell Patent No. 2,042,880, and since quite small percentages often give remarkably improved results it is seldom of extreme importance that the addition agents be oil-soluble in all proportions. Also, certain compounds are of value as gelling or bodying agents when used inv amounts greater than are strictly soluble.

When the materials included within the conconnection, it should be noted that certain of the addition agents contemplated for use herein may be employed for the additional purpose of bodying or thickening the lubricant to which they are era], the "chlorinated" or chlorine-bearing" templation of my invention, as above defined, are

used as or in lubricants in the manner hereinbefore specified, it will be understood that other agents may be employed in conjunction therewith, so long as such other agents are not incompatible with the materials comprising my invention. Thus, for example, other agents designed to supplement the characteristics of the materials herein identified in providing a, lubricant having any of the previously named desirable characteristics may be employed, as well as agents which supply any of such characteristics which are not provided by the particular materials used in practicing my invention.

The materials above identified, contemplated for use in practicing my invention have been particularly referred to as useful as or in lubricants. It will be observed that they may likewise be employed to advantage as addition agents in fuels employed in internal combustion engines, either in their pure state or admixed with other fuel addition agents or included as a constituent in a lubricant added to the fuel. Certain of these materials are, as previously indicated, particularly suitable for use in fuels on account of their ability to withstand high temperatures.

While the lubricating compositions which have been described herein as illustrating one embodiment of the invention have been generally referred to as oils," i. e., liquids, this invention is, however, also applicable to the solid and semisolid types of lubricants commonly referred to in the trade as greases, bodied oils, etc. In this species will be found preferable on account of the lower cost and generally satisfactory effectiveness of chlorine as compared with the other halogens. The fluorinated or fluorine-bearing species of certain of the named materials will be found especially useful on account of the inherently greater stability of certain of the fluorine compounds, as compared with the other halogens.

It will also be found that two or more halogens such as, for example, chlorine and bromine or chlorine and fluorine, may be employed together in the same molecule in a halogenated" or "halogen-bearing" substance where the same is thus identified in the foregoing description.

Included in the foregoing description of this invention, reference has been made to the use of the condensation products resulting from the reaction between certain-named constituents. It will be observed that the constituents themselves which have been previously referred to as useful in the preparation of the condensation product are, in some cases, useful as addition agents in lubricating compositions. It is therefore to be understood that this invention contemplates the production of lubricating compositions, the properties of which affecting its use as a lubricant have been improved by incorporating therein a minor amount of any of the named constituents which have been previously referred to as constituents useful as reactants to form the condensationproducts. In certain cases, these constituents, as such, may be added separately to the lubricating composition or may be included therein by virtue of their inclusion in the reaction product, i. e., if the condensation reaction is not carried to completion and the condensation product purified by removal of the unreacted constituents.

The foregoing is to be understood as referring not necessarily to the combined presence of the two types of unreacted constituents in the composition but is to include also the use as the sole addition agent in a lubricating composition of any of the named constituents of both classes.

In the foregoing description of this invention, general reference has been made to lubricating compositions including certain particularly identified materials. It will be understood that in general the compositions resulting from the present invention will generally, on account of cost of materials used,- consist largely of lubricating oils such as, for example, mineral oils, animal oils and vegetable oils. A mixture of two or more of such oils along with the named addition agents will be found highly useful for certain purposes. As a specific example, a mixture of a mineral oil, a fatty oil such as lard oil, and an addition agent selected from those described will be found to possess improved properties for certain purposes with respect to oiliness by virtue of the presence therein of the fatty oil.

The oil base particular use for which the ultimate compositionis designed. When the lubricating compositions of my invention are designed for the lubrication of automobiles, the oil base will of course preferably consist of a refined mineral lubricating oil .of lubricating viscosity for. the particular point of application. In other words, the conventional gear oil may be used for the lubrication of gears, for example, mineral oil having a viscosity range of from an S. A. E. 80 to an S. A. E. 140. Generally a lighter, more highly refined oil may be used in the crank case, such as a motor oil having a viscosity range of from an S. A. E. 10 to an S. A. E. 50.

This invention is applicable to lubricating compositions in which the base may consist either entirely or in part of synthetic oils, hydrogenated oils, and voltolized oils.

The oil base may also desirably contain other well known constituents such as those which improve the oillness, pour point, cold test, and oxidation properties, etc., of the oil. In general, compositions of my invention may be employed with any commercially available addition agents for the above defined purposes since they are generally compatible with the same in the amounts usually used.

In the foregoing references to mineral oil is meant to be included oils refined from any of the various crude oils, for example, those obtained from the Pennsylvania, Mid-Continent, and Gulf Coastal fields. and oils refined by any of the usual refining processes including distillation, solvent extraction, acid treatment, clay treatment, dewaxing, etc.

The viscosity of the base oil chosen should be such that the final composition will have viscosity suitable for the particular use for which it is intended. The viscosity of the final composition may, in certain cases, be advantageously less than that which would be selected in the case ofthe use of a base oil alone. These viscosities may range from those of spindle oils or lighter through the range usually selected for crankcase lubricants, to those of heavy gear oils, cylinder oils, and the like, or even heavier.

Many of the addition agents contemplated by this invention are particularly suitable for use with mineral oils containing sufiicient quantities of wax or wax-like constituents to cause them, without the use of an addition agent, to cease to flow at low temperatures.

Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated in any of the following claims or the equivalent of such be employed.

1 therefore particularly point out and distinctly claim as my invention:

1. An extreme pressure lubricant comprising a major proportion of mineral lubricating oil and an aromatic compound containing (a) an aromatic nucleus, (b) an aliphatic substituent containing more than three carbon atoms, and (c) an inorganic substituent containing an element of the class consisting of oxygen and sulphur, said compound present in an amount suflicient to increase the load carrying capacity of the composition so as to prevent seizure and scoring of the bearing lubricant thereby when operated under conditions of boundary lubrication.

2. An extreme pressure lubricant comprising a major proportion of mineral lubricating oil and an aromatic compound containing (a) an arcmatic nucleus, (1:) an aliphatic substituent containing more than ten carbon atoms, and (c) an inorganic substituent containing an element of the class consisting of oxygen and sulphur, said compound present in an amount sufllcient to increase the load carrying capacity of the composition so as to prevent seizure and scoring of the bearing lubricant thereby when operated under conditions of boundary lubrication.

3. An extreme pressure lubricant comprising a major proportion of mineral lubricating oil and an aromatic compound containing both an allphatic substituent and a sulphur bearing inorganic substituent, said compound present in an amount sumcient to increase the load carrying capacity of the composition so as to prevent seizure and scoring of the bearing lubricant thereby when operated under conditions of boundary lubrication.

4. An extreme pressure lubricant comprising a major proportion of mineral lubricating oil and an aromatic compound containing both an allphatic substituent having at least three carbon atoms and an oxygen-bearing inorganic substituent, said compound present in an amount willcient to increase the load carrying capacity of the composition so as to prevent seizure and scoring of the bearing lubricant thereby when operated under conditions of boundary lubrication.

5. An extreme pressure lubricant comprising a major proportion of mineral lubricating oil and an aromatic compound containing both an allphatic substituent having at least three carbon atoms and a sulphur bearing inorganic substituout, said compound present in an amount sufllcient to increase the load carrying capacity 01 the composition so as to prevent seizure and scoring of the bearing lubricant thereby when operated under conditions of boundary lubrication.

6. A lubricating composition comprising an aromatic compound containing (a) an aromatic nucleus, (b) an aliphatic substituent. and (c) the radicle XM where X is of the class consisting of oxygen and sulphur and M is aluminum.

7. A lubricating composition comprising an aromatic compound containing (a) an aromatic nucleus, (b) an aliphatic substituent. and (c) the radicle X--M where X is of the class consisting of oxygen and sulphur and M is a metal selected from the class consisting of cobalt and nickel.

8. An extreme pressure lubricant comprising a major proportion of mineral lubricating oil and a halogen bearing aromatic compound containing both an aliphatic substituent and an inorganic substituent containing an element of the class consisting of oxygen and sulphur, said compound present in an amount suilicient to increase the load carrying capacity of the composition so as to prevent seizure and scoring of the bearing lubricant thereby when operated under conditions of boundary lubrication. 9. A lubricating composition comprising a major proportion of mineral lubricating oil and from .001% to 20% of an aromatic compound containing (a) an aromatic nucleus, (b) an aliphatic substituent having at least 3 carbon atoms. and (c) an inorganic substituent containing the radical 0-M where 0 is oxygen and M is a metal.

10. A lubricating composition comprising a major proportion of mineral lubricating oil and from .001% to 20% of an aromatic compound containing (a) an aromatic nucleus, (b) an aliphatic substituent having at least 3 carbon atoms, and (c) an inorganic substituent containing the rad- 21 Y ical E-M where S is sulphur and M is a mm.

emu. r. PRU'I'I'ON.

REFERENCES crnm The following feferences file of this patent:

are of rcord in the 5' UNITED sums mum-s Number Prutton Nov. 28, 1940 

